Structure provided with zeolite separation membrane, method for producing same, method for separating mixed fluids and device for separating mixed fluids

Abstract

There is provided a zeolite separation membrane-provided article having gaps or pores larger than pores inherent to zeolite crystals and controlled within an appropriate range and being capable of achieving both high permeability and high separability for components with small difference in adsorption properties or a component having a smaller molecular diameter than the diameter of the pores, a method for producing the same, a method for separating mixed fluids, and a device for separating mixed fluids. The zeolite separation membrane-provided article is provided with a zeolite membrane having an N 2 gas permeation speed at room temperature of 1.0×10 −6 mol·m −2 ·s −1 ·Pa −1 or more and a permeation speed ratio of 1,3,5-trimethylbenzene/N 2 at room temperature of 0.17 or more and being free from dyeing caused by the impregnation with Rhodamine B.

1. A zeolite membrane-provided article provided with a zeolite membrane, the zeolite membrane-provided article having an N 2  gas permeation speed at room temperature of 1.0×10 −6  mol·m −2 ·s −1 ·Pa −1  or more and a permeation speed ratio of 1,3,5-trimethylbenzene/N 2  at room temperature of 0.17 or more, wherein the zeolite membrane-provided article is free from dyeing caused by the impregnation with Rhodamine B, and wherein pore sizes of pores inherent to zeolite crystals are 0.76 nm or less and pore sizes of pores other than the pores inherent to zeolite crystals are 0.76 nm to 2 nm. 
     
     
       2. The zeolite membrane-provided article according to  claim 1 , wherein the zeolite membrane is formed on a surface of a support of a porous material. 
     
     
       3. The zeolite membrane-provided article according to  claim 1 , wherein the zeolite membrane is a MFI membrane. 
     
     
       4. The zeolite membrane-provided article according to  claim 1 , wherein the zeolite membrane is a silicalite membrane. 
     
     
       5. The zeolite membrane-provided article according to  claim 1 , which is used for separation of a mixed fluid of two or more different components. 
     
     
       6. A method for producing a zeolite membrane-provided article comprising:
 a seed crystal-forming step of putting a seeding sol containing silica, water, and a structure directing agent and a support in a pressure resistant container in a state that the support is immersed in the seeding sol, followed by heating the inside of the pressure resistant container to form zeolite seed crystals on a surface of the support; 
 a membrane-forming step of growing the zeolite seed crystal to form a dense zeolite membrane containing the structure directing agent on the surface of the support; and 
 a removal step of removing the structure directing agent from the dense zeolite membrane; 
 wherein the removal treatment in the removal step is performed by a heat treatment; 
 wherein the heat treatment is performed in a maximum temperature range of 400 to 1000° C. and includes a temperature rise step at a temperature rise speed of 0.1° C./min. or more and a temperature fall step at a temperature fall speed of 0.5° C./min. or more; 
 whereby the zeolite membrane-provided article provided with a zeolite membrane has an N 2  gas permeation speed at room temperature of 1.0×10 −6  mol·m −2 ·s −1 ·Pa −1  or more, a permeation speed ratio of 1,3,5-trimethylbenzene/N 2  at room temperature of 0.17 or more, and is free from dyeing caused by the impregnation with Rhodamine B, and wherein pore sizes of pores inherent to zeolite crystals are 0.76 nm or less and pore sizes of pores other than the pores inherent to zeolite crystals are 0.76 nm to 2 nm. 
 
     
     
       7. The method for producing a zeolite membrane-provided article according to  claim 6 , wherein the zeolite membrane is a MFI membrane. 
     
     
       8. The method for producing a zeolite membrane-provided article according to  claim 6 , wherein the zeolite membrane is a silicalite membrane. 
     
     
       9. A method for separating a mixed fluid, wherein a mixed fluid of two or more different components is separated by using a zeolite membrane-provided article according to  claim 1 . 
     
     
       10. A mixed fluid separation device having a zeolite separation membrane-provided article according to  claim 1  and comprising: a separation section for separating a raw material side space from a permeation side space by a porous substrate, a supply section for supplying a mixed fluid to the raw material side space, a permeation collection section for collecting permeation liquid and/or permeation gas having penetrated the zeolite membrane. 
     
     
       11. The method for producing a zeolite membrane-provided article according to  claim 7 , wherein the zeolite membrane is a silicalite membrane.